JPH01215023A - Surface treatment and device therefor - Google Patents

Abstract

PURPOSE:To prevent damage, contamination and a temperature rise, and to enable surface treatment having high throughput by mounting a surface (an activating surface) activating at least one part of gas particles in the same chamber as a sample. CONSTITUTION:An activating surface 2 represents a surface through which activated particles R are formed by the contact of gas particles M, and Al2O3, SiO2, C, Si or Si-C having excellent heat resistance and chemical reaction resistance or a metal such as W, Mo, Ta, Ti, Ni, Nb, Pt, etc., or these alloy or mixture is used as the material of the activating surface 2. The directions of activated particles R projected to the surface of a sample 3 are controlled, the activated particles R are projected to the surface of the sample, the temperature of the sample is kept at a temperature lower than 400 deg.C and a mask pattern is transferred to a substrate without undercut by introducing gas molecules M, elevating the temperature of the activating surface at 100-3000 deg.C and installing a collimator 9 between the activating surface 2 and the sample 3.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a dry process (dry processing) method and apparatus for treating an integral surface, and is particularly suitable for producing semiconductor devices with no damage, no contamination, and high selectivity. The present invention relates to a surface treatment method and apparatus capable of realizing a low-temperature, high-throughput (processing speed) process.

(Prior Art) Japanese Patent Laid-Open No. 62-35521 discloses a surface treatment apparatus that realizes a damage-free, non-contaminating, highly selective, and low-humidity dry process suitable for manufacturing semiconductor devices. In this patent, a gas is chemically activated by heating it in a high-temperature furnace, and then it is ejected into a vacuum to form an active particle beam.The surface treatment is performed using this active particle beam in the apparatus of the above patent. It is a function.

[ilM to be solved by the invention] In the above conventional technology, gas particles that are reflected without reacting on the sample surface are exhausted as they are and are not activated again. Therefore, the gas particles are used for surface treatment. The problem was that efficiency was low and high throughput could not be obtained.

It is an object of the present invention to provide a surface treatment method and apparatus that is free from damage, contamination, temperature rise, and has a high throughput. Here, 1. surface treatment refers to removing substances on the sample surface (etching), depositing substances on the sample surface (deposition, epitaxy), and modifying the sample surface substances (oxidation, nitridation, etc.).

doping, etc.).

[Means for solving the problem] The above purpose is to install a surface that activates at least a portion of gas particles (activation surface) in the same chamber (reaction chamber) as the sample, and to This is achieved by surface treatment by injecting active particles onto the sample surface. 2 points A here
, B are in the same room, are the gas pressures measured at A and B the same?

When the difference is small (for example, within 10 times, although the allowable difference varies depending on the situation), this method and device reactivate gas particles that did not react on the sample surface. The active particles can be incident on the sample surface multiple times, and throughput can be dramatically improved.

The surface that activates the gas particles can be a heated surface, a catalytic surface, or a combination of these, but it is generally not necessary to use a surface that is heated to a high temperature, a surface that has a catalytic effect, or a combination thereof. Any surface that activates can be used.

Here, particles (or gas particles) are atoms.

Refers to molecules or positively or negatively ionized versions thereof. In addition, active particles particularly mean chemically active particles, and specifically include radicals (particles with unpaired electrons or dangling bonds), and particles at electronic, rotational, or vibrational levels. It refers to particles in which at least one of them is excited, or particles whose translational energy per degree of freedom is larger than the energy equivalent to normal room temperature (about 20° C.) (about 1.3×10″″e v).

To achieve directional surface treatment, a collimator can be placed between the activation surface and the sample surface. This makes it possible to align the directions of active particles incident on the sample surface, thereby realizing directional surface treatment.

[Effect]

Since the activated surface is in the same chamber as the sample surface, the gas particles are activated multiple times on average and impinge on the sample surface, thereby improving throughput. In addition, the activated surface chemically activates gas particles, and the total energy possessed by the active particles (the sum of the main energies released by the active particles on the sample surface) can be suppressed to 10 av or less, resulting in less damage and less damage. Low pollution.

It is the same as the conventional example (Japanese Unexamined Patent Publication No. 62-35521) that can achieve highly selective and warm surface treatment.

The collimator has the function of aligning the flight direction of active particles,
Achieve directional surface treatment.

〔Example〕

Hereinafter, one embodiment of the present invention will be explained with reference to FIG. 1. An activated surface 2 and a sample 3 are placed in a reaction chamber 1. For the sample 3, the 6 reaction gases held on the sample stage 4 are introduced into the reaction chamber 1 via the valve 5, and the 6 reaction gases exhausted from the exhaust port 6 are of a single type. The activated surface 2, which can be a gas or a mixture of gases, is heated or cooled if necessary by activated surface temperature control means 7. Also, the sample
3 is also heated or cooled by the sample temperature control means 8 as necessary. The sample temperature control means 8 may also serve as the sample stage 4, or may be installed separately from the sample stage 4. Further, if necessary, a collimator 9 can be installed between the activated surface 2 and the sample 3, and the surface temperature of the collimator 9 is controlled by a collimator temperature control means 10 as necessary. Further, the collimator 9 and the sample stage 4 can be driven one-dimensionally, two-dimensionally, or even three-dimensionally as necessary. The activated surface 2 can also be actuated as well, if required. Furthermore, if necessary, a mechanism for cooling the walls of the reaction chamber 1 can be provided.

The activated surface 2 is a surface that becomes activated particles R when gas particles M touch it, as shown in FIG.

What is meant by 1 particle and active particle here is as stated in the previous section (means for solving the problem).Specifically, a high temperature solid surface or a solid surface with catalytic action is activated on activated surface 2. The material for the activated surface is Altos (alumina, ruby), which has excellent heat resistance and chemical reaction resistance.

Sift (quartz, crystal), C (graphite, polycrystalline carbon, diamond), Si (single crystal.

Polycrystalline) and Si-C (alloy or mixture of Si and C) are suitable. In addition, in order to utilize the catalytic action, materials with a large surface work function such as W and Mo are used.

Metals such as Ta, Ti, Ni, Nb, and Pt, as well as alloys or mixtures thereof, can also be used as the material for the activated surface 2. Materials with low radiant heat are particularly useful in practice, since high temperature surfaces can be obtained with low heating power. Suitable materials for this will vary depending on the temperature of the activated surface, for example,
When using stainless steel #Zr0t e W#
Ties #cordierite, Si01, etc. are suitable. The activated surface can be formed on a solid surface or a thin film formed on a solid, or on a liquid surface.

Radical active particles R can be formed by heating the activated surface 2 to a high temperature and surface thermally decomposing the gas molecules M6. For example, if Fg gas is introduced as M and the temperature Ta of the activated surface is raised to 500°C or higher. More than 10% of the F2 molecules incident on the activated surface 2 are F! →2F ... Decomposes by the reaction of ■ to form radical active particles F. Also 1M
Similarly, when C11z is used and Ta is raised to 800°C or higher, 10% or more of the CQx molecules incident on the activated surface 2.

A thermal decomposition reaction of Cat-h2CQ-@ forms radical active particles CQ. Furthermore, if a high temperature surface ('ra>1500℃) is used, O, On,
Active particles such as N can be formed. When forming such active particles, the material for the activation surface is AQioa, Si, which has excellent heat resistance and chemical reaction resistance.
Ox, C, Si-C, etc. are suitable. Also, W,
Mo, Ta.

Even with metals such as Ti, Nb, and Pt, if the temperature Ta of the activated surface is made sufficiently high (for example, Ta>2000° C.), radical active particles R can be formed without the activated surface being eroded. However, if Ta is too high, the surface material will evaporate, so even in this case, T&≦3000℃
It needs to be. By this, active particles R of F- and CQ- can be formed.

By controlling Ta lower than in the above case, the electronic level can be rotated 9 times without decomposing 1M.

At least one of the vibrational levels is excited, or the translational energy per degree of freedom is equal to room temperature energy (approximately 1.
For example, using Fz gas particles as M, Ta=100~15
By controlling the temperature to 00°C, active particles R of pz hot molecules (denoted as F-) can be formed. Furthermore, when using CQz gas particles as 1M and controlling 'ra=100 to 2000℃, C
Active particles R of hot molecules of Qz (denoted as Cjlz fist) can be formed. Similarly, M is FCa.

If molecules containing halogen elements such as NFa, CFa, SFs, etc. are used, hot molecules of these molecules can be formed, and these hot molecules containing halogen elements can be effectively used in etching treatment. In addition, by using as M a molecule containing the element that you want to deposit on the sample surface, hot molecules suitable for film deposition can be formed.For example, when depositing Si,
When depositing S i H4eSi, H, G, As, P, B, GaHs, As Ha, P H
a, BHs, etc., or a mixed gas thereof can be used. Further, hot molecules such as 02 and N can be used for oxidation and nitridation.

The above is a method of supplying the particles M as a gas into the reaction chamber 1 to form the activated particles R, but the activated particles R are formed on the activated surface 2 or within the substance forming the activated surface. Activated particles R can also be formed by pre-applying or impregnating particles M for 0, for example on the W surface.

Apply NaCjl and heat the W surface (112100
0°C), Na, Cn, Na÷.

Active particles such as base 0 can be formed.

In the following example, CQz gas was introduced into the reaction chamber 1,
Forming hot molecules of Cf1x as activated particles R1,
Regarding etching the sample surface.

This will be explained in detail. FIG. 3 shows a cross-sectional view of the sample to be etched. A mask having a pattern desired to be formed on the substrate surface (or a pattern that is the original form of the desired pattern) is formed on the surface of the sample by etching. The material for forming the mask is preferably one that is difficult to etch, such as SiOx (silicon oxide).

Polymer films such as SiaNa (silicon nitride) and photoresist are suitable. The material to be etched can be the surface of the substrate material or a thin film formed on the substrate surface.

The material of the activated surface 2 is AΩ, which does not easily react with Cap.
ZOa and Sins are suitable. Furthermore, since C and Si-C remove Ca radicals formed on the surface in the form of CCa, they are effective in reducing the effect of Ca radicals during etching. For the same reason, W, Mo, T
a.Ti.

Metal surfaces such as Nb and Pt can also be used as activation surfaces. The activated surface can be heated indirectly or directly.
e heatlng) by Ta = 100~20
It is heated and controlled to reach 00°C. By providing the activated surface temperature control means 7 with a cooling function as well as a heating function, humidity control can be performed with high precision.

CQ staying in reaction chamber 1! Some of the molecules enter the activated surface 2 and become activated particles R of hot molecules and are desorbed from the surface. Let the angle formed with the normal be θ,
If the number of active particles desorbed per unit time within a solid angle dΩ in the direction of a certain θ is N(θ)dΩ, then N(θ) is expressed as N(θ)=Nocosθ...■ sNo is the value of N(θ) when θ=0.

Also, the amount of C formed in unit time on the activated surface of unit area is
41 The number N of active particles of z is C11 in 1 reaction chamber 1.
zProportional to gas pressure (molecules when mixed gas) Pci,
N is approximately expressed as N=6.5 x 10”Pcs* ・=■. Here, the units of N and Pct□ are pieces/
(sac-Cm”) and Torr.

The CΩ2 active particles R (hereinafter referred to as
(denoted as Cl1s)) flies inside the reaction chamber and reaches the surface of sample 3. At this time, if the gas pressure Pr in the reaction chamber (P r = P CAI when only Cut gas is used) is high, the CΩ2 umbrella will collide with atmospheric gas particles in the reaction chamber before reaching the sample surface, and the flight direction will change. It will be disturbed.

In order to prevent such collisions, when the distance between the activated surface 2 and the surface of the sample 1 is a, and the mean free path of CQx in one reaction chamber is λ, n≦λ... ■It must be. On the other hand, the mean free path λ is inversely proportional to the gas pressure Pr, and is expressed as follows: 1=5×10−”/Pr·=@ Here, the unit of λtPr is am.

It is expressed in Torr. Also, since the gas pressure during normal processing is Pr≧I X 10-'Torr, ■,
■From the formula, it is desirable that a≧500cm.Furthermore, if the gas flow rate is increased, P≧I X 10-'Torr,
Generally, Q≦50e-. On the other hand, when a becomes too small, Cnx enters the space between the activated surface and the sample surface.
Inconveniences arise because the gas supply and reaction products are not sufficiently exhausted. To prevent this kind of thing, 0
If we take the total of 0 or more, which is preferably 21mm, it is desirable that 1m-≦sac≦500cm ,,, ■, generally, 1m-≦sac≦550cm
...■ is desirable.

By installing the collimator 9 between the activated surface 2 and the sample 3 while satisfying the conditions of (1) or (2) or 0, the active particles CII x・
direction can be controlled.

The action of the collimator will be explained below. The collimator is specifically made of a plate with one or many holes as shown in FIG. The temperature of the material making up the holes is controlled by heating or cooling if necessary, and is generally often cooled, for example water cooling can be used, and to further cool it to a lower temperature. Cooling with liquid nitrogen can also be used. It is desirable that the material of the collimator has a large thermal conductivity coefficient and excellent chemical reaction resistance.For example, AQ, Cu, quartz, alumina, etc. can be used. Or a material with good thermal conductivity (AΩ
, Cu, etc.), the surface (especially the inner wall of the pores) is coated with a chemically resistant substance (
It is also possible to use a material coated with quartz, alumina, Teflon, polymeric material @Au@Pt, etc.).

The active cord R, which passes through the hole of the collimator without touching the inner wall of the hole, can pass through the collimator while remaining active. However, when the active particle R enters the inner wall of the hole, its translational energy and internal energy (vibration, rotation, and electronic level energy) are taken away by the inner wall, and it is deexcited and returns to the inactive particle M.

Alternatively, it is adsorbed to the inner wall and does not come out into the gas phase again. Furthermore, if R is a charged particle, it will be neutralized by entering the inner wall of the hole and will no longer be a charged particle.The reason why the active particle R passes through the collimator while remaining active is due to the material of the collimator. Only when passing through a hole without touching the surface. That is, only the active particles R flying in the direction along the hole pass through the collimator while remaining active and enter the sample surface. At this time, the spread angle α in the flight direction of the active particles passing through the collimator is tan α = d/h, where the diameter of the hole is d and the length of the hole is h.
... becomes ■. α is the angle between the direction n of the pores and the flying direction of the active particles.

The CQz hot molecules formed in this way (CQz molecules) are incident on the sample surface, and the sample temperature T
If s is kept lower than a certain predetermined temperature, the mask pattern can be transferred to the substrate without undercut along the incident direction of CΩ2m. Fig. 5(a) shows the situation in which a Si substrate is etched in this way. Fig. 5 shows a case where CII Even in this case, the same effect as described below can be expected, and etching along the incident direction of CQZ* can be realized. The reason why etching can be performed without undercutting is as follows. That is, when Cf1z* is incident on the sample surface, a part of it becomes S i + -CII
t* →S i C41m↑ ・A reaction product SICfi is produced by a reaction such as aS.

(n=1 to 4). The Si surface is etched by desorption of this reaction product from the surface. However, if some of the incident C11z- is desorbed (reflected) from the surface without reacting.

This reflected C112 molecule remains an active particle (i.e. CΩ
2ψ), it will be incident on the sidewall of the pattern, etching the sidewall, and forming an undercut (see Figure 5(b)). However, if the sample surface attitude Ts is kept at a low temperature, Then, when the CQz umbrella reflects, its translation,
The pattern can be transferred to CII z molecules that are deexcited and inactive due to internal energy being absorbed by the substrate surface without undercutting. In order to perform such etching without undercutting, experiments have shown that it is desirable that Ts≦400°C.

According to experiments, when the temperature Ta of the activated surface is set to 800°C to form Cnt*, and the sample temperature T$ is set to 200°C,
The probability that Cas& incident on the sample surface will undergo a [phase] reaction is approximately 2×10 −8 . Also, Pca*= p, =
If I X 10-'Torr, then from formula 0.

N=6.6X10” pieces/(sec-am”),
Assume that 10% of this passes through the collimator.

6.6 x 1056 per unit time and unit area on the sample surface
/ (sac-cw+") CQl will be incident. This Cnz. will undergo a [phase] reaction, and the reaction product S
When etching is performed by forming i(lla), the realized etching speed t (ns+/Sin) is E
= 400 (nm/win), and at this time, in order to perform directional etching, a≦5C from formulas ■ and ■.
It must be ll.

If a Si wafer with a diameter of 6 inches is etched at the above etching speed, the etching rate will be 1.2X10 per second per reaction.
19 CΩ2 molecules will be consumed. this is,
The flow rate is 308 ccm. Therefore, about 10% of the C j2 x gas molecules introduced into the reaction chamber 1
To make it responsive.

It is necessary to introduce Caz gas into the reaction chamber at a flow rate of about 300 sccs+. At this time, Pr = I x 10-”
In order to maintain Torr, it is necessary to use a pump with a pumping speed of 3800 M/8. In this case, the CΩ sluggish molecules introduced into the reaction chamber 1 will have an opportunity to enter and react with the sample surface in the form of Ca1 about 50 times on average. This can be seen in the conventional example (Unexamined Japanese Patent Publication No. 62-3
5521), which has the concept of reacting with the surface only once on average, which can be said to be a remarkable feature of the five patents. This is.

This is the reason why high throughput can be achieved with this patent.

Some of the CQ2 molecules are decomposed and ionized on the activated surface 2 to form C
There is a possibility of forming Q-. Therefore, by applying a voltage to the sample using the voltage applying means 11, C
Accelerate or decelerate a- toward the sample (in extreme cases,
As the voltage to be applied, direct current or alternating current (low frequency, high frequency) can be used depending on the purpose. Furthermore, by forming a magnetic field between the activated surface and the sample surface, charged particles CJI- can be effectively transported to the sample surface and further prevented from entering the sample surface. CQ can be effectively achieved by making the direction of the magnetic field lines perpendicular to the sample surface.
- can be transported, and by making them parallel, it is possible to prevent Ca- from entering the sample surface. The strength of the magnetic field is 10-1000
Gauss is suitable.

If NaCa is attached as an impurity to the activated surface,
Na÷ and Ca- are generated from the surface.

Since Na contamination has a significant impact on semiconductor device characteristics,
Preventing Na + from entering the sample surface by the above method is particularly useful in practical terms.

Thermal radiation from the activated surface 2 can heat the sample surface. This will be discussed below. The radiant energy emitted from a unit area of the activated surface is Q=σTa4...0σ:
It is expressed as the emissivity of the activated surface. Using blackbody emissivity ao as σ, a=5.7X10-”(J/(cm”5eck
')), using 'ra=aoo℃=1073k, Q=7.6J/cm"-gec=7.6vatt/c
m'', of which 1/10 is incident on the sample surface, 0.76 watt/am'' of heat will be incident on the sample. For this level of heat.

By cooling the sample stage with water and mounting the sample so as to press it against the sample stage, it is possible to maintain the sample attitude T at 100° C. or lower. If a large amount of heat is incident on the sample surface, fill the space between the sample and the sample stage with gas (preferably an inert gas such as He or Ar) (pressure = 10-" to 10").
It is effective to improve the thermal contact between the sample and the sample stage by adjusting the temperature (appropriately Torr) to prevent sample heating.

The case where Cjlx gas is used as the introduced gas has been described above, but Fx, FCQ, SFe.

A molecular gas containing a halogen element such as NFa or CFa can be used similarly. In addition, although the case where Si is used as the material to be etched has been explained, other materials containing Si, materials containing Ga, As, and P, as well as AQ, Mo, etc.
, WeTa, NbtNi, Ti, and other metals can be similarly etched.

Also, carbon (graphite, polycrystalline carbon).

Etching of organic polymers (diamond) can also be performed in the same way. In this case, it is also effective to use Ox or a molecular gas containing an oxygen element as the introduced gas.

In addition, the method of this embodiment not only involves etching but also oxidation and etching.
It can also be used for surface modification such as nitriding, deposition, epitaxy, etc. Regarding such an application, it can be considered as described in another patent (Japanese Unexamined Patent Publication No. 61-113775), and the feature of this patent is that the throughput is higher than that of the conventional example.

Figure 6 shows the cross-sectional area of a part of the activated surface.By forming irregularities on the surface as shown in Figure 6, the gas particles M will collide with the activated surface many times, resulting in activation. efficiency can be increased. The dimension a of the unevenness is several
The following are valid:

FIGS. 7(a), (b), and (c) show cross sections of the activated surface. By forming the activated surface into a curved shape, it becomes possible to control the flux (particle flux) of active particles incident on the sample surface, which is effective in improving the uniformity of processing speed. At this time, it is desirable that the shape of the curved surface be rotationally symmetrical with respect to the central axis of the activated surface (normal to the surface at the center). A shape that returns to its original position.

As the size of the sample increases, it becomes difficult to supply gas particles to the center of the sample and to exhaust reaction products from the center. As a result, the uniformity of processing speed deteriorates. To prevent this, it is effective to introduce the introduced gas from inside the activated surface (through the activated surface). In Figure 8(a), the gas is introduced from the center of the activated surface;
), the gas is introduced through the entire porous or multi-perforated activated surface.

It is also possible to use the method or apparatus of the invention in combination with other surface treatment techniques, for example.

It is also possible to further improve the throughput by processing the surface in advance using a surface treatment technique using plasma or a photoion beam, and then using the method and apparatus of the present invention. It is also possible to combine in the reverse order of the above.

When the activated surface 2 is used at a high temperature, it is necessary to cool the activated surface 2 to near a variable temperature before leaking atmospheric pressure into the reaction chamber 1 for replacing the sample 3. Thereafter, it is necessary to exchange the sample and bring the activated surface to a high temperature again. This is to prevent the high temperature activated surface from deteriorating due to contact with the atmosphere. However, in this case, 1
Time is wasted in cooling and reheating the surface, reducing throughput. To prevent this, reaction chamber 1
In addition, it is effective to provide a preliminary chamber for sample introduction and to connect both chambers with a gate valve.

By doing so, after putting a replacement sample into the preliminary chamber and evacuating the preliminary chamber, the gate valve can be opened and the sample can be exchanged with a processed sample. As a result, samples can be exchanged without exposing the activated surface to the atmosphere, and the time required for cooling and reheating the activated surface can be shortened. A similar effect can also be achieved by providing a gate valve between the activated surface and the sample and replacing the sample with the gate valve closed.

〔Effect of the invention〕

According to the present invention, since gas particles are incident on the sample surface which has been activated multiple times on average, high-throughput surface treatment can be achieved. In addition, since low-energy active particles are used, there is less damage and less pollution.

Highly selective and low temperature surface treatment can be achieved. Also.

By using a collimator, directional surface treatment can be achieved.

[Brief explanation of the drawing]

FIG. 1 is a sectional view of an embodiment of the present invention, FIG. 2 is a sectional view of the vicinity of the activated surface, and FIG. 3 is a sectional view of an etching sample.
FIG. 4 is a partial sectional view of the collimator. FIG. 5 is a cross-sectional view of the etched sample, FIG. 6 is a partial cross-sectional view of the activated surface, and FIG. 7 is a cross-sectional view of the activated surface.
FIG. 8 is a sectional view near the activated surface. l... Reaction chamber, 2... Activated surface, 3... Sample,
4... Sample stand, 5... Valve, 6... Exhaust port, 7
Activation surface temperature control means, 8... Sample temperature control means, 9... Collimator, 10... Collimator temperature control means, 11... 5 Figures etc. 4 buds 5 buds 6 diagrams Barrel 7 figure

Claims (1)

[Scope of Claims] 1. A surface treatment method characterized by placing an activated surface on which active particles are formed and a sample to be surface treated in the same room. 2. The surface treatment method according to claim 1, further comprising introducing a gas for forming active particles into the chamber. 3. The surface treatment method according to claim 1, wherein the activated surface is made of a surface having a temperature higher than room temperature or a surface having a catalytic action. 4. The material of the activated surface is SiO_2, Al_2O
_3, C, Si, Si-C, W, Mo, Ta, Ti, N
2. The surface treatment method according to claim 1, wherein the material is any one of i, Nb, and Pt, or a mixture or alloy thereof. 5. The temperature Ta of the activated surface is Ta=100-3
2. The surface treatment method according to claim 1, wherein the temperature is 000°C. 6. Temperature Ta of the activated surface and temperature Ts of the sample surface
2. The surface treatment method according to claim 1, wherein: are controlled independently of each other. 7. The surface treatment method according to claim 6, wherein the Ta and Ts satisfy Ta>Ts or Ts≦400°C. 8. The surface treatment method according to claim 1, wherein the activated surface is an uneven surface. 9. The surface treatment method according to claim 1, wherein the activated surface is a flat or curved surface. 10. The surface treatment method according to claim 1, wherein the activated surface has a rotationally symmetrical shape. 11. The method of claim 2, wherein the gas is introduced through the activated surface. 12. The surface treatment method according to claim 1, wherein a part of the surface of the sample is covered with a mask. 13. The surface treatment method according to claim 1, wherein a DC or AC voltage is applied to the sample. 14. The surface treatment method according to claim 1, further comprising applying a magnetic field between the activated surface and the sample. 15. The surface treatment method according to claim 2, wherein the gas is composed of molecules containing a halogen element, or the molecules are part of the constituent particles. 16. The surface treatment method according to claim 15, wherein the surface treatment is etching. 17. The surface treatment method according to claim 2, wherein the gas is composed of molecules containing oxygen or nitrogen elements, or the molecules are part of the constituent particles. 18. The surface treatment method according to claim 17, wherein the surface treatment is oxidation or nitridation. 19. The surface treatment method according to claim 1, wherein the surface treatment is deposition or epitaxy. 20. The surface treatment method according to claim 1, wherein the distance between the activated surface and the surface of the sample is shorter than the mean free path of the active particles. 21. The surface treatment method according to claim 1, wherein the distance between the activated surface and the surface of the sample is 50 cm to 1 mm. 22. The surface treatment method according to claim 1, further comprising providing a collimator between the activated surface and the sample. 23. The surface treatment method according to claim 22, wherein the collimator is cooled. 24. The surface treatment method according to claim 1, further comprising providing a gate valve between the activated surface and the sample. 25. The surface treatment method according to claim 1, further comprising a preliminary evacuation chamber for exchanging the sample in addition to said chamber, and said chamber and said preliminary evacuation chamber are connected by a gate valve. 26. A surface treatment apparatus comprising a reaction chamber, an activated surface provided in the chamber, a sample provided in the chamber, and a sample stage. 27. The surface treatment apparatus according to claim 26, further comprising means for introducing gas into the reaction chamber. 28. The surface treatment apparatus according to claim 26, further comprising a collimator provided between the activated surface and the sample.